American Chemical Society
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Total Synthesis of the Lycopodium Alkaloid Serratezomine A Using Free Radical-Mediated Vinyl Amination to Prepare a β‑Stannyl Enamine Linchpin

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journal contribution
posted on 2013-02-01, 00:00 authored by Julie A. Pigza, Jeong-Seok Han, Aroop Chandra, Daniel Mutnick, Maren Pink, Jeffrey N. Johnston
Serratezomine A is a member of the structurally diverse class of compounds known as the Lycopodium alkaloids. The key supporting studies and successful total synthesis of serratezomine A are described in this account. Significant features of the synthesis include the first application of free radical mediated vinyl amination and Hwu’s oxidative allylation in a total synthesis and an intramolecular lactonization via a transannular SNi reaction. Minimal use of protecting groups and the highly diastereoselective formation of a hindered, quaternary stereocenter using an umpolung allylation are also highlights from a strategy perspective. Observation of quaternary carbon epimerization via a retro-Mannich/Mannich sequence highlights the additional challenge presented by the axial alcohol at C8 in serratezomine A.